Phthalamide derivatives

ABSTRACT

This invention relates to novel phthalamide derivatives of formula (I) 
     
       
         
         
             
             
         
       
         
         
           
             wherein R 1 , R 2 , R 3 , R 4 , and R 5  have the meanings given in the disclosure, to processes for their preparation, and to their use as insecticidal agents in agricultural and horticultural field.

The present patent application has been filed under 35 U.S.C. 371 as anational stage application of PCT/EP2003/006105, filed Jun. 11, 2003,which was published in English as International Patent Publication WO2004/000796 on Dec. 31, 2003, which is entitled to the right of priorityof Japanese Patent Application 2002-180028, filed Jun. 20, 2002.

It is already known that certain phthalamide derivatives show an actionas insecticide (cf.: EP 0 919 542-A2, EP 1 006 107-A2, WO 01/00575, WO01/00599, WO 01/21576).

Further, it is already known that certain phthalamide derivatives showan action as pharmaceutical (cf.: EP 0 119 428-A2).

There have now been found novel phthalamide derivatives of the formula(I)

wherein

-   R¹ represents alkyl which may be optionally halogen-substituted,-   R² represents alkyl which may be optionally substituted or    cycloalkyl which may be optionally substituted,-   R³ represents hydrogen atom, halogen, or alkyl which may be    optionally halogen-substituted,-   R⁴ represents hydrogen atom, halogen-substituted alkyl,    halogen-substituted alkoxy, halogen-substituted phenyl, or    halogen-substituted phenoxy, and-   R⁵ represents hydrogen atom, halogen, or alkyl which may be    optionally halogen-substituted.

Depending on the nature and the number of substituents, the compounds ofthe formula (I) may be present as geometrical and/or optical isomers,regioisomers or configurational isomers or isomer mixtures thereof ofvarying composition. What is claimed by the invention are both the pureisomers and the isomer mixtures.

The compounds of the formula (I), according to the invention, can beobtained by a process in which

-   a) compounds of the formula (II)

-   -   wherein R¹, R³, R⁴ and R⁵ have the same definitions as        aforementioned, are reacted with compounds of the formula (III)        H₂N—R²  (III)    -   wherein R² has the same definition as aforementioned, in the        presence of inert solvents, and if appropriate, in the presence        of a base,        or

-   b) compounds of the formula (IV)

-   -   wherein R¹ and R² have the same definitions as aforementioned,        are reacted with compounds of the formula (V)

-   -   wherein R³, R⁴ and R⁵ have the same definitions as        aforementioned, in the presence of inert solvents, and if        appropriate, in the presence of an acid catalyst,        or

-   c) compounds of the formula (VI)

-   -   wherein R¹, R³, R⁴ and R⁵ have the same definitions as        aforementioned, are reacted with compounds of the formula (III),        H₂N—R²  (III)    -   wherein R² has the same definition as aforementioned, in the        presence of inert solvents, and if appropriate, in the presence        of a acid catalyst,        or

-   d) in case of preparing the compounds of the formula (I) in which R²    represents alkylsulfinylalkyl or alkylsulfonylalkyl: compounds of    the formula (Id)

-   -   wherein    -   R^(2d) represents alkylthioalkyl,    -   R¹, R³, R⁴ and R⁵ have the same definitions as aforementioned,        are reacted with an oxidizing agent, in the presence of inert        solvents.

The phthalamide derivatives of the formula (I) provided by the presentinvention show a strong insecticidal action.

According to the present invention the phthalamide derivatives of theformula (I) are included conceptually in the compounds represented bythe general formula described in EP 0 919 542-A2 or EP 1 006 107-A2. Insaid publications, however, the phthalamide derivatives of the formula(I) of the present invention are not specifically disclosed.

The compounds of the formula (I) of the present invention surprisinglyshow very strong insecticidal action, compared with the compoundsspecifically described in the above-mentioned patent publications, whichare similar to the formula (I) of the present invention and particularlyexhibit excellent insecticidal action against lepidopteran harmfulinsects. Moreover, the compounds of the formula (I) of the presentinvention show systemic insecticidal action.

In the present specification, “halogen” and halogen part in “alkyl whichmay be halogen-substituted”, “halogen-substituted alkyl”,“halogen-substituted alkoxy”, “halogen-substituted phenyl” and“halogen-substituted phenoxy” represents fluoro, chloro, bromo or iodo,and is preferably fluoro, chloro or bromo.

“Alkyl” and alkyl part in each group “alkoxy”, “alkylthio”,“alkylsulfinyl” and “alkylsulfonyl” can be a straight-chain orbranched-chain and there can be mentioned, for example, methyl, ethyl,n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-, iso-, neo-,tert-pentyl, 2-methylbutyl, n-, iso- or sec-hexyl, etc.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

“Halogen-substituted alkyl” represents a straight-chain orbranched-chain alkyl, at least one of which hydrogen is substituted withhalogen, and there can be mentioned, for example, C₁₋₆ alkyl substitutedwith 1–9 fluoro and/or chloro, and as its specific examples there can bementioned, difluoromethyl, trifluoromethyl, 2-fluoroethyl,2-chloroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl,1,1,2,2,2-pentafluoroethyl, 2-chloro-1,1,2-trifluoroethyl,3-fluoropropyl, 3-chloropropyl, 1-methyl-2,2,2-trifluoroethyl,2,2,3,3,3-pentafluoropropyl, 1,2,2,3,3,3-hexafluoropropyl,perfluoroisopropyl, perfluorobutyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl,3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc.

Halogen-substituted alkyl part in “halogen-substituted alkoxy” can be ofthe same definition as the aforementioned “halogen-substituted alkyl”and as “halogen-substituted alkoxy” there can be mentioned specifically,for example, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy,2-chloroethoxy, 2-bromoethoxy, 2,2,2-trifluoroethoxy, etc.

“Halogen-substituted phenyl” and halogen-substituted phenyl part in“halogen-substituted phenoxy” can represent phenyl substituted with 1-3,preferably 1-2 of the aforementioned “halogen” and as its specificexamples there can be mentioned 2-, 3- or 4-fluorophenyl, 2-, 3- or4-chlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenyl, etc.

In the compounds of the aforementioned formula (I), preferably

-   R¹ represents C₁₋₆ alkyl which may be optionally fluoro-substituted,    chloro-substituted or bromo-substituted,-   R² represents C₁₋₆ alkyl which may be optionally fluoro-substituted,    chloro-substituted, bromo-substituted, C₁₋₄ alkoxy-substituted, C₁₋₄    alkylthio-substituted, C₁₋₄ alkylsulfinyl-substituted, or C₁₋₄    alkylsulfonyl-substituted, or represents C₃₋₆ cycloalkyl which may    be optionally halogen-substituted or C₁₋₄ alkyl-substituted,-   R³ represents hydrogen atom or halogen, or represents C₁₋₆ alkyl    which may be optionally fluoro-substituted, chloro-substituted or    bromo-substituted,-   R⁴ represents hydrogen atom, halogen-substituted C₁₋₆ alkyl,    halogen-substituted C₁₋₆ alkoxy, halogen-substituted phenyl, or    halogen-substituted phenoxy, and-   R⁵ represents hydrogen atom or halogen, or represents C₁₋₆ alkyl    which may be optionally fluoro-substituted, chloro-substituted or    bromo-substituted.

In the compounds of the aforementioned formula (I), more preferably

-   R¹ represents methyl, ethyl, propyl or tri-fluoromethyl,-   R² represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,    sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl,    n-hexyl, isohexyl, sec-hexyl, methylthiomethyl, ethylthiomethyl,    methylthioethyl, ethylthioethyl, methylthiopropyl, ethylthiopropyl,    methylthiobutyl, ethylthiobutyl, methylthiopentyl, ethylthiopentyl,    methylsulfinylmethyl, ethylsulfinylmethyl, methylsulfinylethyl,    ethylsulfinylethyl, methylsulfinylpropyl, ethylsulfinylpropyl,    methylsulfinylbutyl, ethylsulfinylbutyl, methylsulfinylpentyl,    ethylsulfinylpentyl, methylsulfonylmethyl, ethylsulfonylmethyl,    methylsulfonylethyl, ethylsulfonylethyl, methylsulfonylpropyl,    ethylsulfonylpropyl, methylsulfonylbutyl, ethylsulfonylbutyl,    methylsulfonylpentyl, ethylsulfonylpentyl, or represents    cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which    may be optionally substituted with fluoro, chloro, bromo, methyl or    ethyl,-   R³ represents hydrogen atom, fluoro, chloro, bromo, methyl, ethyl or    trifluoromethyl,-   R⁴ represents fluoro, chloro or bromo, or represents methyl, ethyl,    n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,    methoxy, ethoxy, n-propoxy or isopropoxy, each of which may be    optionally partially substituted with at least one fluoro,    perfluoro-substituted, or substituted with at least one fluoro and 1    or 2 chloro,-   R⁵ represents hydrogen atom, fluoro, chloro or bromo, or represents    methyl or ethyl, each of which may be optionally fluoro-substituted    or chloro-substituted.

In the compounds of the aforementioned formula (I), further particularlypreferably

-   R¹ represents methyl or ethyl,-   R² represents isopropyl, tert-butyl, 1-methyl-2-(methylthio)ethyl,    1,1-dimethyl-2-(methylthio)ethyl, 1-methyl-2-(methylsulfinyl)ethyl,    1,1-dimethyl-2-(methylsulfinyl)ethyl,    1-methyl-2-(methylsulfonyl)ethyl or    1,1-dimethyl-2-(methylsulfonyl)ethyl,-   R³ represents methyl,-   R⁴ represents perfluoroisopropyl, and-   R⁵ represents hydrogen atom.

The aforementioned preparation process (a) can be illustrated by thefollowing reaction formula in case, for example,N-(4-heptafluoroisoproyl-2-methylphenyl)-3-methanesulfonyloxyphthalimideand isopropylamine are used as the starting materials.

The aforementioned preparation process (b) can be illustrated by thefollowing reaction formula in case, for example,6-methanesulfonyloxy-N-isopropylphthalisoimide and4-heptafluoroisopropyl-2-methylaniline are used as starting materials.

The aforementioned preparation process (c) can be illustrated by thefollowing reaction formula in case, for example,N-(4-heptafluoroisoproyl-2-methylphenyl)-3-methanesulfonyloxyphthalisoimideand isopropylamine are used as starting materials.

The aforementioned preparation process (d) can be illustrated by thefollowing reaction formula in case, for example,N²-[1,1-dimethyl-2-(methylthio)ethyl]-N¹-(4-heptafluoroisoproyl-2-methylphenyl)-3-methanesulfonyloxyphthalamideand m-chloroperbenzoic acid are used as starting materials.

The compounds of the formula (U), the starting materials in theabove-mentioned preparation process (a), are novel compounds, which arenot yet described in the literature, and can be prepared, for example,

by reacting compounds of the formula (VII)

wherein R³, R⁴ and R⁵ have the same definitions as aforementioned, withcompounds of the formula (VIII)R¹SO₂Cl  (VIII)wherein R¹ has the same definition as aforementioned (cf. e.g.Tetrahedron Letters 1988, 29, 5595–5598).

The compounds of the above-mentioned formula (VII), part of which arenovel compounds, that are not yet described in the literature, can beprepared, for example,

by reacting per se known 3-hydroxyphthalic anhydride

with compounds of the aforementioned formula (V)

wherein R³, R⁴ and R⁵ have the same definitions as aforementioned (cfe.g. JP 61-246161).

The compounds of the aforementioned formula (V) are known compounds andare available on the market or can be prepared by known methods (cf J.Org. Chem. 1964, 29, 1, Angew. Chem. Int. Ed. Engl., 1985, 24, 871, JP11-302233).

The compounds of the above-mentioned formula (VIII) are compounds wellknown in the field of organic chemistry and as their specific examplesthere can be mentioned, for example, methanesulfonyl chloride,ethanesulfonyl chloride, trifluoromethanesulfonyl chloride,2,2,2-trifluoroethanesulfonyl chloride, etc.

The compounds of the formula (II) used as the starting materials in thepreparation process (a) there can be mentioned as follows:

-   3-methanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalimide,-   methanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalimide,-   3-methanesulfonyloxy-N-(4-pentafluoroethylphenyl)phthalimide,-   N-(4-heptafluoroisopropylphenyl)-3-methanesulfonyloxyphthalimide,-   3-methanesulfonyloxy-N-(2-methyl-4-trifluoromethylphenyl)phthalinude,-   3-methanesulfonyloxy-N-(2-methyl-4-trifluoromethoxyphenyl)phthalimide,-   3-methanesulfonyloxy-N-(2-methyl-4-pentafluoroethylphenyl)phthalimide,-   N-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalimide,-   3-methanesulfonyloxy-N-(2,3,4-trichlorophenyl)phthalimide,-   3-ethanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalimide,-   3-ethanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalimide,-   3-ethanesulfonyloxy-N-(4-pentafluoroethylphenyl)phthalimide,-   3-ethanesulfonyloxy-N-(4-heptafluoroisopropylphenyl)phthalimide,-   3-ethanesulfonyloxy-N-(2-methyl-4-trifluoromethylphenyl)phthalimide,-   3-ethanesulfonyloxy-N-(2-methyl-4-trifluoromethoxyphenyl)phthalimide,-   3-ethanesulfonyloxy-N-(2-methyl-4-pentafluoroethylphenyl)phthalimide,-   3-ethanesulfonyloxy-N-(4-heptafluoroisopropyl-2-methylphenyl)phthalimide,-   3-ethanesulfonyloxy-N-(2,3,4-trichlorophenyl)phthalimide,-   3-trifluoromethanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalimide,-   3-trifluoromethanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalimide,-   N-(4-pentafluoroethylphenyl)-3-trifluoromethanesulfonyloxyphthalimide,-   N-(4-heptafluoroisopropylphenyl)-3-trifluoromethanesulfonyloxyphthalimide,-   N-(2-methyl-4-trifluoromethylphenyl)-3-trifluoromethanesulfonyloxyphthalimide,-   N-(2-methyl-4-trifluoromethoxyphenyl)-3-trifluoromethanesulfonyloxyphthalimide,-   N-(2-methyl-4-pentafluoroethylphenyl)-3-trifluoromethanesulfonyloxyphthalimide,-   N-(4-heptafluoroisopropyl-2-methylphenyl)-3-trifluoromethanesulfonyloxyphthalimide,-   N-(2,3,4-trichlorophenyl)-3-trifluoromethanesulfonyloxyphthalimide,    and so on.

The compounds of the formula (VII) used in the preparation of theaforementioned formula (II) there can be mentioned as follws:

-   3-hydroxy-N-(4-trifluoromethylphenyl)phthalimide,-   3-hydroxy-N-(4-trifluoromethoxyphenyl)phthalimide,-   3-hydroxy-N-(4-pentafluoroethylphenyl)phthalimide,-   N-(4-heptafluoroisopropylphenyl)-3-hydroxyphthalimide,-   3-hydroxy-N-(2-methyl-4-trifluoromethylphenyl)phthalimide,-   3-hydroxy-N-(2-methyl-4-trifluoromethoxyphenyl)phthalimide,-   3-hydroxy-N-(2-methyl-4-pentafluoroethylphenyl)phthalimide,-   N-(4-heptafluoroisopropyl-2-methylphenyl)-3-hydroxyphthalimide,-   3-hydroxy-N-(2,3,4-trichlorophenyl)phthalimide, and so on.

The compounds of the formula (V) used in the preparation of theaforementioned formula (VII) there can be mentioned as follows:

-   4-trifluoromethylaniline,-   4-trifluoromethoxyaniline,-   4-pentafluoroethylaniline,-   4-heptafluoroisopropylaniline,-   2-methyl-4-trifluoromethylaniline,-   2-methyl-4-trifluoromethoxyaniline,-   2-methyl-4-pentafluoroethylaniline,-   4-heptafluoroisopropyl-2-methylaniline,-   2,3,4-trichloroaniline, and so on.

The compounds of the formula (III), the starting materials in theabove-mentioned preparation process (a), are compounds well known in thefield of organic chemistry and can be prepared according to the processdescribed in DE-A 20 45 905, WO 01/23350 Pamphlet, etc.

The compounds of the formula (III) used as the starting materials in thepreparation process (a) there can be mentioned as follows:

-   n-propylamine,-   isopropylamine,-   n-butylamine,-   sec-butylamine,-   isobutylamine,-   tert-butylamine,-   tert-amylamine,-   cyclopropylamine,-   cyclopentylamine,-   cyclohexylamine,-   2-(methylthio)ethylamine,-   2-(ethylthio)ethylamine,-   1-methyl-2-(methylthio)ethylamine,-   1,1-dimethyl-2-(methylthio)ethylamine, and so on.

The compounds of the formula (IV), the starting materials in theabove-mentioned preparation process (b), are novel compounds which arenot described in the literature yet and can be prepared

by reacting compounds of the formula (IX)

wherein R¹ and R² have the same definitions as aforementioned,in the presence of a condensing agent or an acid binding agent(cf. e.g. J. Med. Chem. 1967, 10, 982)

The compounds of the above-mentioned formula (IX) are also novelcompounds which are not yet described in the literature and can beprepared

by reacting compounds of the formula (X)

wherein R¹ has the same definition as aforementioned with compounds ofthe formula (III)H₂N—R²   (III)wherein R² has the same definition as aforementioned(cf. e.g. J. Org. Chem. 1981, 46, 175).

The compounds of the above-mentioned formula (X) are also novelcompounds which are not yet described in the literature and can beprepared

by reacting the per se known 3-hydroxyphthalic anhydride with compoundsof formula (VIII)R¹SO₂Cl  (VIII)wherein R¹ has the same definition as aforementioned (cf. e.g.Tetrahedron Lett. 1988, 29, 5595–5598).

The compounds of the formula (IV) used as starting materials in thepreparation process (b) there can be mentioned as follows:

-   6-methanesulfonyloxy-N-n-propylphthalisoimide,-   N-isopropyl-6-methanesulfonyloxyphthalisoimide,-   N-n-butyl-6-methanesulfonyloxyphthalisoimide,-   N-sec-butyl-6-methanesulfonyloxyphthalisoimide,-   N-isobutyl-6-methanesulfonyloxyphthalisoimide,-   N-tert-butyl-6-methanesulfonyloxyphthalisoimide,-   6-methanesulfonyloxy-N-[2-(methylthio)ethyl]phthalisoimide,-   N-[2-(ethylthio)ethyl]-6-methanesulfonyloxyphthalisoimide,-   6-methanesulfonyloxy-N-[1-methyl-2-(methylthio)ethyl]phthalisoimide,-   N-[1,1-dimethyl-2-(methylthio)ethyl]-6-methanesulfonyloxyphthalisoimide,-   6-ethanesulfonyloxy-N-n-propylphthalisoimide,-   6-ethanesulfonyloxy-N-isopropylphthalisoimide,-   N-n-butyl-6-ethanesulfonyloxyphthalisoimide,-   N-sec-butyl-6-ethanesulfonyloxyphthalisoimide,-   6-ethanesulfonyloxy-N-isobutylphthalisoimide,-   N-tert-butyl-6-ethanesulfonyloxyphthalisoimide,-   6-ethanesulfonyloxy-N-[2-(methylthio)ethyl]phthalisoimide,-   6-ethanesulfonyloxy-N-[2-(ethylthio)ethyl]phthalisoimide,-   6-ethanesulfonyloxy-N-[1-methyl-2-(methylthio)ethyl]phthalisoimide,-   N-[1,1-dimethyl-2-(methylthio)ethyl]-6-ethanesulfonyloxyphthalisoimide,-   N-n-propyl-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-isopropyl-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-n-butyl-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-sec-butyl-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-isobutyl-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-tert-butyl-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-[2-(methylthio)ethyl]-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-[2-(ethylthio)ethyl]-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-[1-methyl-2-(methylthio)ethyl]-6-trifluoromethanesulfonyloxyphthalisoimide,-   N-[1,1-dimethyl-2-(methylthio)ethyl]-6-trifluoromethanesulfonyloxyphthalisoimide,    and so on.

The compounds of the formula (IX) used in the preparation of theaforementioned formula (IV) there can be mentioned as follows:

-   3-methanesulfonyloxy-N-n-propylphthalamic acid,-   N-isopropyl-3-methanesulfonyloxyphthalamic acid,-   N-n-butyl-3-methanesulfonyloxyphthalamic acid,-   N-sec-butyl-3-methanesulfonyloxyphthalamic acid,-   N-isobutyl-3-methanesulfonyloxyphthalamic acid,-   N-t-butyl-3-methanesulfonyloxyphthalamic acid,-   3-methanesulfonyloxy-N-[2-(methylthio)ethyl]phthalamic acid,-   N-[2-(ethylthio)ethyl]-3-methanesulfonyloxyphthalamic acid,-   3-methanesulfonyloxy-N-[1-methyl-2-(methylthio)ethyl]phthalamic    acid,-   N-[1,1-di-methyl-2-(methylthio)ethyl]-3-methanesulfonyloxyphthalamic    acid,-   3-ethanesulfonyloxy-N-n-propylphthalamic acid,-   3-ethanesulfonyloxy-N-isopropylphthalamic acid,-   N-n-butyl-3-ethanesulfonyloxyphthalamic acid,-   N-sec-butyl-3-ethanesulfonyloxyphthalamic acid,-   3-ethanesulfonyloxy-N-isobutylphthalamic acid,-   N-t-butyl-3-ethanesulfonyloxyphthalamic acid,-   3-ethanesulfonyloxy-N-[2-(methylthio)ethyl]phthalamic acid,-   3-ethanesulfonyloxy-N-[2-(ethylthio)ethyl]phthalamic acid,-   3-ethanesulfonyloxy-N-[1-methyl-2-(methylthio)ethyl]phthalamic acid,-   N-[1,1-di-methyl-2-(methylthio)ethyl]-3-ethanesulfonyloxyphthalamic    acid,-   N-n-propyl-3-trifluoromethanesulfonyloxyphthalamic acid,-   N-isopropyl-3-trifluoromethanesulfonyloxyphthalamic acid,-   N-n-butyl-3-trifluoromethanesulfonyloxyphthalamic acid,-   N-sec-butyl-3-trifluoromethanesulfonyloxyphthalamic acid,-   N-isobutyl-3-trifluoromethanesulfonyloxyphthalamic acid,-   N-t-butyl-3-trifluoromethanesulfonyloxyphthalamic acid,-   N-[2-(methylthio)ethyl]-3-trifluoromethanesulfonyloxyphthalamic    acid,-   N-[2-(ethylthio)ethyl]-3-trifluoromethanesulfonyloxyphthalamic acid,-   N-[1-methyl-2-(methylthio)ethyl]-3-trifluoromethanesulfonyloxyphthalamic    acid,-   N-[1,1-dimethyl-2-(methylthio)ethyl]-3-trifluoromethanesulfonyloxyphthalamic    acid, and so on.

As the specific examples of the condensing agent or acid binding agentused in the preparation of the compounds of the aforementioned formula(IX) there can be mentioned as follows:

As condensing agent there can be mentioned, for example, Mukaiyama'sreagent (2-chloro-N-methylpyridinium iodide), DCC(1,3-dicyclohexylcarbodiimide), CDI (carbonyl diimidazole),trifluoroacetic anhydride, methyl chlorocarbonate, and so on.

As acid binding agent there can be mentioned, for example, as organicbase, tertiary amines, dialkylaminoanilines and pyridines, for example,triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA),N,N-dimethylaniline, N,N-diethylaniline, pyridine,4-dimethylaminopyridine (DMAP), etc.; as inorganic base, hydroxides,carbonates, bicarbonates, etc. of alkali metals and alkaline earthmetals, for example, sodium hydrogen carbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide,sodium hydroxide, potassium hydroxide, and so on.

The compounds of the formula (X) used in the preparation of theaforementioned formula (IX) there can be mentioned as follows:

-   3-methanesulfonyloxyphthalic anhydride,-   3-ethanesulfonyloxyphthalic anhydride,-   3-trifluoromethanesulfonyloxyphthalic anhydride,-   3-(2,2,2-trifluoroethane)sulfonyloxyphthalic anhydride, and so on.

The compounds of the formula (VI), the starting materials in theabove-mentioned preparation process (c), are novel compounds which arenot yet described in the literature and can be prepared

by reacting compounds of the formula (XI).

wherein R¹, R³, R⁴ and R⁵ have the same definitions as aforementioned inthe presence of such a condensing agent or an acid binding agents asaforementioned (cf. e.g. J. Med. Chem. 1967, 10, 982).

The compounds of the above-mentioned formula (XI) are also novelcompounds which are not yet described in the literature and can beprepared

by reacting compounds of the formula (X)

wherein R¹ has the same definition as aforementioned with compounds ofthe formula (III)H₂N—R²  (III)wherein R² has the same definition as aforementioned(cf. e.g. J. Org. Chem. 1981, 46, 175).

The compounds of the formula (VI) used as starting materials in theabove-mentioned preparation process (c) there can be mentioned asfollws:

-   3-methanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalisoimide,-   3-methanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalisoimide,-   3-methanesulfonyloxy-N-(4-pentafluoroethylphenyl)phthalisoimide,-   N-(4-heptafluoroisopropylphenyl)-3-methanesulfonyloxyphthalisoimide,-   N-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalisoimide,-   3-methanesulfonyloxy-N-(2,3,4-trichlorophenyl)phthalisoimide,-   3-ethanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalisoimide,-   3-ethanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalisoimide,-   3-ethanesulfonyloxy-N-(4-pentafluoroethylphenyl)phthalisoimide,-   3-ethanesulfonyloxy-N-(4-heptafluoroisopropylphenyl)phthalisoimide,-   3-ethanesulfonyloxy-N-(4-heptafluoroisopropyl-2-methylphenyl)phthalisoimide,-   3-ethanesulfonyloxy-N-(2,3,4-trichlorophenyl)phthalisoimide,-   3-trifluoromethanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalisoimide,-   3-trifluoromethanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalisoimide,-   N-(4-pentafluoroethylphenyl)-3-trifluoromethanesulfonyloxyphthalisoimide,-   N-(4-heptafluoroisopropylphenyl)-3-trifluoromethanesulfonyloxyphthalisoimide,-   N-(4-heptafluoroisopropyl-2-methylphenyl)-3-trifluoromethanesulfonyloxyphthalisoimide,-   N-(2,3,4-trichlorophenyl)-3-methanesulfonyloxyphthalisoimide, etc.

The compounds of the formula (XI) used in the preparation of theaforementioned formula (VI) there can be mentioned as follows:

-   6-methanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalamic acid,-   6-methanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalamic acid,-   6-methanesulfonyloxy-N-(4-pentafluoroethylphenyl)phthalamic acid,-   N-(4-heptafluoroisopropylphenyl)-6-methanesulfonyloxyphthalamic    acid,-   N-(4-heptafluoroisopropyl-2-methylphenyl)-6-methanesulfonyloxyphthalamic    acid,-   6-methanesulfonyloxy-N-(2,3,4-trichlorophenyl)phthalamic acid,-   6-ethanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalamic acid,-   6-ethanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalamic acid,-   6-ethanesulfonyloxy-N-(4-pentafluoroethylphenyli)phthalamic acid,-   6-ethanesulfonyloxy-N-(4-heptafluoroisopropylphenyl)phthalamic acid,-   6-ethanesulfonyloxy-N-(4-heptafluoroisopropyl-2-methylphenyl)phthalamic    acid,-   6-ethanesulfonyloxy-N-(2,3,4-trichlorophenyl)phthalamic acid,-   6-trifluoromethanesulfonyloxy-N-(4-trifluoromethylphenyl)phthalamic    acid,-   6-trifluoromethanesulfonyloxy-N-(4-trifluoromethoxyphenyl)phthalamic    acid,-   N-(4-pentafluoroethylphenyl)-6-trifluoromethanesulfonyloxyphthalamic    acid,-   N-(4-heptafluoroisopropylphenyl)-6-trifluoromethanesulfonyloxyphthalamic    acid,-   N-(4-heptafluoroisopropyl-2-methylphenyl)-6-trifluoromethanesulfonyloxyphthalamic    acid,-   N-(2,3,4-trichlorophenyl)-3-trifluoromethanesulfonyloxyphthalamic    acid, and so on.

The compounds of the formula (Id), the starting materials in theabove-mentioned preparation process (d), correspond to the compounds ofthe formula (I) of the present invention, in which R² is alkylthioalkyl,and can be prepared, for example, according to the aforementionedpreparation processes (a) to (c).

The compounds of the formula (Id) used as starting materials in theabove-mentioned preparation process (d) there can be mentioned asfollows:

-   N²-[1-methyl-2-(methylthio)ethyl]-N¹-(4-trifluoromethoxy-2-methylphenyl)-3-methanesulfonyloxyphthalamide,-   N¹-(4-heptafluoroisopropylphenyl)-N²-[1-methyl-2-(methylthio)ethyl]-3-methanesulfonyloxyphthalamide,-   N¹-(4-heptafluoroisoprppyl-2-methylphenyl)-N²-[1-methyl-2-(methylthio)ethyl]-3-methanesulfonyloxyphthalamide,-   N¹-(4-heptafluoroisopropyl-2-methylphenyl)-N²-[1-methyl-2-(methylthio)ethyl]-3-ethanesulfonyloxyphthalamide,-   N¹-(4-heptafluoroisopropyl-2-methylphenyl)-N²-[1-methyl-2-(methylthio)ethyl]-3-trifluoromethanesulfonyloxyphthalamide,-   N²-[1,1-dimethyl-2-(methylthio)ethyl]-N¹-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalamide,-   N²-[1,1-dimethyl-2-(methylthio)ethyl]-N¹-(4-heptafluoroisopropyl-2-methylphenyl)-3-ethanesulfonyloxyphthalamide,-   N²-[1,1-dimethyl-2-(methylthio)ethyl]-N¹-(2,3,4-trichlorophenyl)-3-methanesulfonyloxyphthalamide,    and so on.

As the oxidizing agent used for S-oxidation of the compounds of theformula (Id) in the preparation process (d) there can be mentioned, forexample, m-chloroperbenzoic acid, peracetic acid, potassiummetaperiodate, potassium hydrogen persulfate (trade name: OXONE^(R)),hydrogen peroxide, and so on.

The compounds of the formula (II), formula (IV), formula (VI), formula(IX), formulae (X) and (IX), either starting materials or intermediateproducts in the aforementioned processes (a) to (c) for the preparationof the compounds of the formula (I) of the present invention are allnovel compounds which are not described in the literature yet and arerepresented collectively by the following general formula (XII)

wherein

-   R¹ has the same definition as aforementioned,-   (a) A¹ and A⁴ each represents oxygen atom,    -   A² represents the group NH—R² and A³ represents hydroxy,    -   or    -   A² represents hydroxy and A³ represents the group

-   -   or    -   A², together with A³, represents a group selected from

-   (b) A¹ represents the group N—R²,    -   A², together with A³, represents the group

-   -   and    -   A⁴ represents oxygen atom,    -   or

-   (c) A¹ represents oxygen atom,    -   A², together with A³, represents the group

-   -   and    -   A⁴ represents the group

-   -   wherein R², R³, R⁴ and R⁵ have the same definition as        aforementioned.

The reaction of the aforementioned preparation process (a) can beconducted in an adequate diluent. As examples of the diluent used inthat case there can be mentioned aliphatic, alicyclic and aromatichydrocarbons (may be optionally chlorinated), for example, pentane,hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene,xylene, dichloromethane, chloroform, carbon tetrachloride,1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, forexample, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether,dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycoldimethyl ether (DGM), etc.; esters, for example, ethyl acetate, amylacetate, etc.; acid amides, for example, dimethylformamide (DMF),dimethylacetamide (DMA), N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (HMPA),etc.

The preparation process (a) can be conducted in the presence of a baseand as examples of said base there can be mentioned, for example,tertiary amines, dialkylaminoanilines and pyridines, for example,triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA),N,N-dimethylaniline, N,N-diethylaniline, pyridine,4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2.2.2]octane (DABCO),1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), etc.

The preparation process (a) can be conducted in a substantially widerange of temperature. However, it can be conducted at the temperaturesin a range of generally about −20 to about 150° C., preferably about 10to about 100° C. Although said reaction is conducted desirably undernormal pressure, it can be operated also under elevated pressure orunder reduced pressure.

In conducting the preparation process (a), the aimed compounds of theformula (I) can be obtained, for example, by reacting 1 to 25 moleamount of the compounds of the formula (III) to 1 mole of the compoundsof the formula (II).

The reaction of the aforementioned preparation process (b) can beconducted in an adequate diluent, either singly or mixed. As examples ofthe diluent used in that case there can be mentioned water; aliphatic,alicyclic and aromatic hydrocarbons (may be optionally chlorinated), forexample, pentane, hexane, cyclohexane, petroleum ether, ligroine,benzene, toluene, xylene, dichloromethane, chloroform, carbontetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.;ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether,butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF),diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example,acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example,ethyl acetate, amyl acetate, etc.

The preparation process (b) can be conducted in the presence of an acidcatalyst and as examples of said acid catalyst there can be mentionedmineral acids, for example, hydrochloric acid, sulfuric acid, etc.;organic acids, for example, acetic acid, trifluoroacetic acid, propionicacid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonicacid, etc.

The preparation process (b) can be conducted in a substantially widerange of temperature. However, it can be conducted at the temperaturesin a range of generally about −20 to about 100° C., preferably about 0to about 100° C. Although said reaction is conducted desirably undernormal pressure, it can be operated also under elevated pressure orunder reduced pressure.

In conducting the preparation process (b), the aimed compounds of theformula (I) can be obtained, for example, by reacting 1 to 1.5 moleamount of the compounds of the formula (V) to 1 mole of the compounds ofthe formula (IV) in a diluent, for example, acetonitrile.

In conducting the preparation process (b), the compound of the formula(I) can be obtained also by conducting reactions continuously in onepot, starting from 3-hydroxyphthalic anhydride without isolating thecompounds of the formula (X), the compounds of the formula (IX) and thecompounds of the formula (IV).

The reaction of the aforementioned preparation process (c) can beconducted in an adequate diluent, either singly or mixed. As examples ofthe diluent used in that case there can be mentioned water; aliphatic,alicyclic and aromatic hydrocarbons (may be optionally chlorinated), forexample, pentane, hexane, cyclohexane, petroleum ether, ligroine,benzene, toluene, xylene, dichloromethane, chloroform, carbontetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.;ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether,butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF),diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example,acetonitrile, propionitrile, acrylonitrile etc.; esters, for example,ethyl acetate, amyl acetate, etc.

The preparation process (c) can be conducted in the presence of an acidcatalyst and as examples of said acid catalyst there can be mentionedrmineral acids, for example, hydrochloric acid, sulfuric acid, etc.;organic acids, for example, acetic acid, trifluoroacetic acid, propionicacid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonicacid, etc.

The preparation process (c) can be conducted in a substantially widerange of temperature. However, it can be conducted at the temperaturesin a range of generally about −20 to about 100° C., preferably about 0to about 100° C. Although said reaction is conducted desirably undernormal pressure, it can be operated also under elevated pressure orunder reduced pressure.

In conducting the preparation process (c), the aimed compounds of theformula (I) can be obtained, for example, by reacting 1–2 mole amount ofthe compounds of the formula (III) to 1 mole of the compounds of theformula (VI) in a diluent, for example, acetonitrile.

In conducting the preparation process (c), the compounds of the formula(I) can be obtained also by continuously conducting reactions in onepot, starting from 3-hydroxyphthalic anhydride without isolating thecompounds of the formula (X), the compounds of the formula (XI) and thecompounds of the formula (VI).

The reaction of the aforementioned preparation process (d) can beconducted in an adequate diluent. As examples of the diluent used inthat case there can be mentioned water; aliphatic, alicyclic andaromatic hydrocarbons (may be optionally chlorinated), for example,benzene, toluene, xylene, dichloromethane, chloroform, carbontetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.;alcohols, for example, methanol, ethanol, isopropanol, butanol, etc.;acids, for example, formic acid, acetic acid, etc.

The preparation process (d) can be conducted in a substantially widerange of temperature. However, it can be conducted at the temperaturesin a range of generally about −50 to about 150° C., preferably about −10to about 100° C. Although said reaction is conducted desirably undernormal pressure, it can be operated also under elevated pressure orunder reduced pressure.

In conducting the preparation process (d), the aimed compounds of theaforementioned formula (I), in case R² represents alkylsulfinylalkyl oralkylsulfonylalkyl, can be obtained, for example, by reacting 1–5 moleamount of an oxidizing agent, for example, m-chloroperbenzoic acid to 1mole of a compound of the formula (Id) in a diluent, for example,dichloromethane.

The compounds of the formula (I) of the present invention show stronginsecticidal action. They can, therefore, be used as insecticidalagents. And the active compounds of the formula (I) of the presentinvention exhibit exact controlling effect against harmful insectswithout phytotoxicity against cultured plants. The compounds of thepresent invention can be used for controlling a wide variety of pests,for example, harmful sucking insects, biting insects and otherplant-parasitic pests, stored grain pests, hygienic pests, etc. andapplied for their extermination.

As examples of such pests there can be mentioned the following pests:

-   -   As insects, there can be mentioned coleoptera, for example,

-   Callosobruchus Chinensis, Sitophilus zeamais, Tribolium castaneum,    Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala    rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Manochamus    alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus;    Lepidoptera, for example,

-   Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera    litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis,    Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis    fucosa, Galleria mellonella, Plutella maculipennis, Heliothis    virescens, Phyllocnistis citrella;    Hemiptera, for example,

-   Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki,    Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii,    Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex    lectularius, Trialeurodes vaporariorum, Psylla spp.;    Orthoptera, for example,

-   Blatella germanica, Periplaneta americana, Gryllotalpa africana,    Locusta migratoria migratoriodes;    Homoptera, for example,

-   Reticulitermes speratus, Coptoternes formosanus;    Diptera, for example,

-   Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens,    Anopheles slnensis, Culex tritaeniorhynchus, etc.

Moreover, as mites there can be mentioned, for example,

-   Tetranychus telarius, Tetranychus urticae, Panonychus citri, Aculops    pelekassi, Tarsonemus spp. etc.

Furthermore, as nematodes there can be mentioned, for example,

-   Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et    Kiyohara, Aphelenchoides basseyi, Heterodera glycines, Pratylenchus    spp. etc.

In addition, in the field of veterinary medicine, the novel compounds ofthe present invention can be effectively used against various harmfulanimal-parasitic pests (endoparasites and ectoparasites), for example,insects and helminthes. As examples of such animal-parasitic pests therecan be mentioned the following pests:

As insects there can be mentioned, for example,

-   Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp.,    Ctenocephalides canis, etc.

As mites there can be mentioned, for example,

-   Ornithodoros spp., Ixodes spp., Boophilus spp., etc.

In the present invention substances having insecticidal action againstpests, which include all of them; are in some cases called collectivelyas insecticides

The active compounds of the present invention can be made into customaryformulation forms, when they are used as insecticides. As formulationforms there can be mentioned, for example, solutions, emulsions,wettable powders, water dispersible granules, suspensions, powders,foaming agents, pastes, tablets, granules, aerosols, activecompound-impregnated natural and synthetic substances, microcapsules,seed coating agents, formulations used with burning equipment (asburning equipment, for example, fumigation and smoking cartridges, cans,coils, etc.), ULV [cold mist, warm mist], etc.

These formulations can be prepared according to per se known methods,for example, by mixing the active compounds with extenders, namelyliquid diluents; liquefied gas diluents; solid diluents or carriers, andoptionally by using surface-active agents, namely emulsifiers and/ordispersants and/or foam-forming agents.

In case water is used as extender, for example, organic solvents can beused also as auxiliary solvents.

As liquid diluents or carriers there can be mentioned, for example,aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthaleneetc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (forexample, chlorobenzenes, ethylene chlorides, methylene chloride, etc.),aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (forexample, mineral oil fractions etc.)], alcohols (for example, butanol,glycols and their ethers, esters, etc.), ketones (for example, acetone,methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.),strongly polar solvents (for example, dimethylformamide, dimethylsulfoxide, etc.), and water.

Liquefied gas diluents or carriers are substances that are gases atnormal temperature and pressure and there can be mentioned, for example,aerosol propellants such as butane, propane, nitrogen gas, carbondioxide, halogenated hydrocarbons.

As solid diluents there can be mentioned, for example, ground naturalminerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite,montmorillonite, diatomaceous earth, etc.), ground synthetic minerals(for example, highly dispersed silicic acid, alumina, silicates, etc.).

As solid carriers for granules there can be mentioned, for example,crushed and fractionated rocks (for example, calcite, marble, pumice,sepiolite, dolomite, etc.) synthetic granules of inorganic and organicmeals, particles of organic materials (for example, saw dust, coconutshells, maize cobs, tobacco stalks etc.) etc.

As emulsifiers and/or foam-forming agents there can be mentioned, forexample, nonionic and anionic emulsifiers [for example, polyoxyethylenefatty acid esters, polyoxyethylene fatty acid alcohol ethers (forexample, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates,arylsulfonates, etc.)], albumin hydrolysis products, etc.

Dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Tackifiers can also be used in formulations (powders, granules,emulsifiable concentrates). As said tackifiers there can be mentioned,for example, carboxymethyl cellulose, natural and synthetic polymers(for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.).

Colorants can also be used. As said colorants there can be mentioned,for example, inorganic pigments (for example, iron oxide, titaniumoxide, Prussian Blue etc,), organic dyestuffs such as alizarindyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and furthertraces nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

Said formulations can contain the aforementioned active components ofthe amount in the range of generally 0.1–95% by weight, preferably0.5–90% by weight.

The active compounds of the formula (I) of the present invention canexist also as a mixed agent with other active compounds, for example,insecticides, poisonous baits, bactericides, miticides, nematicides,fungicides, growth regulators or herbicides in the form of theircommercially useful formulations or in the application forms preparedfrom such formulations. Here, as the above-mentioned insecticides, therecan be mentioned, for example, organophosphorous agents, carbanateagents, carboxylate type chemicals, chlorinated hydrocarbon typechemicals, insecticidal substances produced by microbes, etc.

Particularly advantageous co-components are, for example, the following:

Fungicides:

-   2-phenylphenol; 8-hydroxyquinoline sulfate; acibenzolar-S -methyl;    aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium;    andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl;    benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril;    benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol;    blasticidin-s; bromuconazole; bupirimate; buthiobate; butylamine;    calcium polysulfide; capsimycin; captafol; captan; carbendazim;    carboxin; carpropamid; carvone; chinomethionate; chlobenthiazone;    chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon;    cyazofamide; cyflufenamide; cymoxanil; cyproconazole; cyprodinil;    cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone;    dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb;    difenoconazole; diflumetorim; dimethirimol; dimethomorph;    dimoxystrobin; diniconazole; diniconazole-m; dinocap; diphenylamine;    dipyrithione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos;    epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone;    fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram;    fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin;    fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil;    flumetover; flumorph; fluoromide; fluoxastrobin; fluquinconazole;    flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol;    folpet; fosetyl-al; fosetyl-sodium; fuberidazole; furalaxyl;    furametpyr; furcarbanil; furmecyclox; guazatine; hexachlorobenzene;    hexaconazole; hymexazol; imazalil; imibencronazole; iminoctadine    triacetate; iminoctadine tris(albesilate); iodocarb; ipconazole;    iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane;    isovaledione; kasugamycin; kresoximmethyl; mancozeb; maneb;    meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-m;    metconazole; methasulfocarb; methfuroxam; metiram; metominostrobin;    metsulfovax; mildiomycin; myclobutanil; myclozolin; natamycin;    nicobifen; nitrothal-isopropyl; noviflumuron; nuarimol; ofurace;    orysastrobin; oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin;    oxyfenthiin; paclobutrazol; pefurazoate; penconazole; pencycuron;    phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins;    polyoxorim; probenazole; prochloraz; procymidone; propamocarb;    propanosine-sodium; propiconazole; propineb; proquinazid;    prothioconazole; pyraclostrobin; pyrazophos; pyrifenox;    pyrimethanil; pyroquilon; pyroxyfur; pyrroInitrine; quinconazole;    quinoxyfen; quintozene; simeconazole; spiroxamine; sulfur;    tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole;    thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram;    tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol;    triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph;    trifloxystrobin; triflumizole; triforine; triticonazole;    uniconazole; validamycin a; vinclozolin; zineb; ziram; zoxamide;    (2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propinyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]-butanamide;    1-(1-naphthalenyl)-1H-pyrrol-2,5-dione;    2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine;    2-amino-4-methyl-n-phenyl-5-thiazolcarboxamide;    2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridincarboxamide;    3,4,5-trichloro-2,6-pyridindicarbonitrile; actinovate;    cis-1-(4-chlorophenyl)-2-(1H-1,2,4triazol-1-yl)-cycloheptanol;    methyl-1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1-Himidazol-5-carboxylate;    mono-potassium carbonate;    n-(6-methoxy-3-pyridinyl)-cyclopropancarboxamide;    n-butyl-8-(1,1-dimethylethyl)-1-oxaspiro[4.5]decan-3-amine; sodium    trathiocarbonate;-   and copper salts and preparations, such as: Bordeaux mixture, copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    cufraneb, copper oxide, mancopper, oxine-copper.    Bactericides:-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,    kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.    Insecticides/acaricides/nematicides:-   abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole,    acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb,    aldoxycarb, allethrin, allethrin 1R-isomers, alpha-cypermethrin    (alphamethrin), amitraz, avermectin, AZ 60541, azadirachtin,    azamethiphos, azinphos-methly, azinphos-ethyl, azocyclotin, Bacillus    popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus    thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus    thuringiensis strain GC-91, Bacillus thuringiensis strain    NCTC-11821, Baculoviruses, Beauveria bassiana, Beauveria tenella,    bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin,    betacypermethrin, bifenazate, bifenthrin, binapacryl, bioallethrin,    bioallethrin-S-cyclopentyl-isomer, bioethanomethrin, biopermethrin,    bioresmethrin, bistrifluron, BPMC, brofenprox, bromophos-ethyl,    bromopropylate, bromfenvinfos (-methyl), BTG-504, BTG-505,    bufencarb, buprofezin, butathiofos, butocarboxim, butoxycarboxim,    butylpyridaben,-   cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion,    carbosulfan, cartap, CGA-50439, chinomethionat, chlordane,    chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr,    chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate,    chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos    (-ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin,    cis-resmethrin, cis-permethrin, clocythrin, cloethocarb,    clofentezine, clothianidine, clothiazoben, codlemone, coumaphos,    cyanofenphos, cyanophos, cycloprene, cycloprothrin, Cydia pomonella,    cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyphenothrin    (1R-trans-isomer), cyromazine, DDT, deltamethrin, demeton-S-methyl,    demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon,    dichlofenthion, dichlorvos, dicofol, dicrotophos, dicyclanil,    diflubenzuron, dimethoate, dimethylvinphos, dinobuton, dinocap,    dinetofuran, diofenolan, disulfoton, docusat-sodium, dofenapyn,    DOWCO-439,-   eflusilanate, emamectin, emarnectin-benzoate, empenthrin    (1R-isomer), endosulfan, Entomopthora spp., EPN, esfenvalerate,    ethiofencarb, ethiprole, ethion, ethoprophos, etofenprox, etoxazole,    etrimfos,-   famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin,    fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb,    fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fensulfothion,    fenthion, fentrifanil, fenvalerate, fipronil, flonicamid,    fluacrypyrim, fluazuron, flubenzimine, flubrocythrinate,    flucycloxuron, flucythrinate, flufenerirn, flufenoxuron, flufenprox,    flumethrin, flupyrazofos, flutenzin (flufenzine), fluvalinate,    fonofos, formetanate, formothion, fosmethilan, fosthiazate,    fubfenprox (fluproxyfen), furathiocarb,-   Gamma-HCH, gossyplure, grandlure, granulosis viruses,-   halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron,    hexythiazox, hydramethylnone, hydroprene,-   IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenphos,    iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion,    ivermectin, Japonilure,-   kadethrin, kempolyederviren, kinoprene, lambda-cyhalothrin, lindane,    lufenuron, malathion, mecarbam, mesulfenfos, metaldehyd,    metam-sodium, methacrifos, methamidophos, metharhizium anisopliae,    metharhizium flavoviride, methidathion, methiocarb, methomyl,    methoprene, methoxychlor, methoxyfenozide, metolcarb, metoxadiazone,    mevinphos, milbemectin, milbemycin, MKI-245, MON-45700,    monocrotophos, moxidectin, MTI-800,-   Naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide,    nicotine, nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250,    NNI-9768, novaluron, noviflumuron,-   OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate,    oxamyl, oxydemeton-methyl,-   paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl),    permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans    isomer), phenthoate, phorate, phosalone, phosmet, phosphamidon,    phosphocarb, phoxim, piperonyl butoxide, pirimicarb,    pirimiphos-methyl, pirimiphos-ethyl, prallethrin, profenofos,    promecarb, propaphos, propargite, propetamphos, propoxur,    prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos,    pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphenthion,    pyridathion, pyrimidifen, pyriproxyfen,-   quinalphos, resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,-   S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad,    spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos,    SZI-121,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos,    teflubenzuron, tefluthrin, temephos, temivinphos, terbam, terbufos,    tetrachlorvinphos, tetradifon, tetramethrin, tetramethrin    (1R-isomer), tetrasul, theta-cypermethrin, thiacloprid,    thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate,    thiodicarb, thiofanox, thiometon, thiosultap-sodium, thuringiensin,    tolfenpyrad, tralocythrin, tralomethrin, transfluthrin, triarathene,    triazamate, triazophos, triazuron, trichlophenidine, trichlorfon,    triflumuron, trimethacarb, vamidothion, vaniliprole, verbutin,    Verticillium lecanii, WL-108477, WL-40027, YI-5201, YI-5301,    YI-5302, XMC, xylylcarb,-   ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901,-   the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the    compound    3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octan-3-carboritrile    (CAS-Reg.-Nr. 185982-80-3) and the corresponding 3-endo-isomer    (CAS-Reg.-Nr. 185984-60-5) (cf. WO 96/37494, WO 98/25923),-   as wells as preparations, which contain insecticidally active plant    extracts, nematodes, fungi or viruses.

A mixture with other known active compounds, such as herbicides, or withfertilizers, growth regulators, safeners or semiochemicals is alsopossible.

Further, the active compounds of the formula (I) of the presentinvention can exist also as a mixed agent with a synergist and suchformulations and application forms can be mentioned as commerciallyuseful. Said synergist itself must not be active, but is a compound thatenhances the action of the active compound.

The content of the active compounds of the formula (I) of the presentinvention in a commercially useful application form can be varied in awide range.

The concentration of the active compounds of the formula (I) of thepresent invention at the time of application can be, for example, in therange of 0.0000001 to 100% by weight, preferably in the range of 0.00001to 1% by weight.

The compounds of the formula (I) of the present invention can be used byusual methods suitable to the application forms.

In case of application against hygienic pests and stored grain pests theactive compounds of the present invention have a good stability againstalkali on a calcific substance and further show an excellent residualeffectiveness in wood and soil.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. By plant cultivars are meant plants having new properties(“traits”), bred either by conventional breeding, by mutagenesis or byrecombinant DNA techniques. They may be cultivars, biotypes andgenotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (i.e. those obtainedby gene-tic engineering) which are to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparted particularly advantageoususeful properties (“traits”) to these plants. Examples of suchproperties are better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products. Further andparticularly emphasized examples of such properties are a better defenceof the plants against animal and microbial pests, such as againstinsects, mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapevines), and particular emphasis isgiven to maize, soya beans, potatoes, cotton and oilseed rape. Traitsthat are emphasized are in particular increased defence of the plantsagainst insects by toxins formed in the plants, in particular thoseformed by the genetic material from Bacillus thuringiensis (for exampleby the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2,Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof)(hereinbelow referred to as “Bt plants”). Traits that are alsoparticularly emphasized are increased defence of plants against fungi,bacteria and viruses by systematic acquired resistance (SAR), systemine,phytoalexins, elicitors and resistance genes and corresponding expressedproteins and toxins. Traits that are furthermore particularly emphasizedare the increased tolerance of the plants to certain herbicidally activecompounds, for example imidazolinones, sulphonylureas, glyphosate orphosphinotricin (for example the “PAT” gene). The genes which impart thedesired traits in question can also be present in combination with oneanother in the transgenic plants. Examples of “Bt plants” which may bementioned are maize varieties, cotton varieties, soya bean varieties andpotato varieties which are sold under the trade names YIELD GARD® (forexample maize, cotton, soya beans), KnockOut® (for example maize),StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) andNewLeaf® (potato). Examples of herbicide-tolerant plants which may bementioned are maize varieties, cotton varieties and soya bean varietieswhich are sold under the trade names Roundup Ready® (tolerance toglyphosate, for example maize, cotton, soya bean), Liberty Link®(tolerance to phosphinotricin, for example oilseed rape), IMI®(tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, forexample maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize). Of course, these statements also apply to plant cultivars havingthese or still to be developed genetic traits, which plants will bedeveloped and/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) or the active compound mixtures according to the invention.The preferred ranges stated above for the active compounds or mixturesalso apply to the treatment of these plants. Particular emphasis isgiven to the treatment of plants with the compounds or the mixturesspecifically mentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattella germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Stemostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) und Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injection(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) according to the invention can be used asformulations (for example powders, emulsions, free-flowingcompositions), which comprise the active compounds according to theinvention in an amount of 1 to 80% by weight, directly or after 100 to10000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention have a strong insecticidal action against insects whichdestroy industrial materials. The following insects may be mentioned asexamples and as preferred—but without a limitation:

Beetles, such as

-   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,    Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex,    Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus,    Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon    aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec.,    Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,    Sinoxylon spec., Dinoderus minutus.    Hymenopterons, such as-   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus    augur.    Termites, such as-   Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,    Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes    lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,    Coptotermes formosanus.    Bristletails, such as Lepisma saccarina.

Industrial materials in the present connection are to be understood asmeaning nonliving materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentsaccording to the invention or mixtures comprising these are to beunderstood as meaning, for example:

building timber, wooden beams, railway sleepers, bridge components, boatjetties, wooden vehicles, boxes, pallets, containers, telegraph poles,wood panelling, wooden window frames and doors, plywood, chipboard,joinery or wooden products which are used quite generally inhouse-building or in building joinery.

The active compounds according to the invention can be used as such, inthe form of concentrates or in generally customary formulations, such aspowders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds according to the invention withat least one solvent or diluent, emulsifier, dispersing agent and/orbinder or fixing agent, a water repellent, if appropriate siccatives andUV stabilizers and if appropriate dyestuffs and pigments, and also otherprocessing auxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by series oftests. In general, however, it is sufficient to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., terpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, provided that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-coumaroneresin, silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or a drying vegetable oil. Alkydresins having an oil content of more than 45% by weight, preferably 50to 68% by weight, are preferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29268. The compounds mentioned in thisdocument are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cyperrnethrin, deltamethrin, permethrin, imidacloprid,NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid,methoxyfenozide and triflumuron, and also fungicides, such asepoxyconazole, hexaconazole, azaconazole, piopiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with saltwateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl(bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganeseethylene-bisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

algicides such as

-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;    fungicides such as-   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,    dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,    tolylfluanid and azoles such as azaconazole, cyproconazole,    epoxyconazole, hexaconazole, metconazole, propiconazole and    tebuconazole;    molluscicides such as-   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and    trimethacarb;    or conventional antifouling active compounds such as-   4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl    sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,    potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,    pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,    2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide    and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730–732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds according to the invention are also suitable forcontrolling animal pests, in particular insects, arachnids and mites,which are found in enclosed spaces such as, for example, dwellings,factory halls, offices, vehicle cabins and the like. They can beemployed alone or in combination with other active compounds andauxiliaries in domestic insecticide products for controlling thesepests. They are active against sensitive and resistant species andagainst all development stages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus andDermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae and Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium and Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus andPorcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus andPolydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina and Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa and Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp. andReticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp. andLiposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais and Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxyscalcitrans and Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella and Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans and Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius faliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp. and Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis and Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus and Triatoma infestans.

In the field of household insecticides, they are used alone or incombination with other suitable active compounds, such as phosphoricacid esters, carbamates, pyrethroids, growth regulators or activecompounds from other known classes of insecticides.

They are used as aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

Then the present invention will be described more specifically byexamples. The present invention, however, should not be restricted onlyto them in any way.

SYNTHESIS EXAMPLES Synthesis Example 1

ToN-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalimide(0.71 g), isopropylamine (1.68 g) was added and stirred at roomtemperature for 4 hours. After finishing the reaction, the excess ofisopropylamine was distilled off under reduced pressure and the obtainedresidue was purified by silica gel column chromatography (gradientelution n-hexane/ethyl acetate=2/1 to 1/1) to obtainN¹(4-heptafluoroisopropyl-2-methylphenyl)-N-2-isopropyl-3-methanesulfonyloxyphthalamide(0.43 g) having the melting point of 168–170° C.

Synthesis Example 2

An acetonitrile solution (20 mL) ofN-isopropyl-6-N-isopropyl-6-methanesulfonyloxyphthalisoimide crudeproduct (1.68 g) and 4-heptafluoroisopropyl-2-methylaniline (1.65 g) wasstirred at 50° C. for 5 hours. After finishing the reaction, the solventwas distilled off under reduced pressure and the obtained residue waspurified by silica gel column chromatography (gradient elutionn-hexane/ethyl acetate=2/1 to 1/1) to obtain the same compound as inSynthesis Example 1 (0.89 g).

Synthesis Example 3

After adding methanesulfonyl chloride (0.69 g) to a 1,2-dichloroethanesolution (14 mL) of 3-hydroxyphthalic anhydride (0.82 g) andtriethylamine (0.76 g) at room temperature, the mixture was stirred at50° C. for 1.5 hours. After bringing the reaction solution to roomtemperature, 1-methyl-2-(methylthio)ethylamine (0.74 g) andtriethylamine (0.76 g) were added under ice cooling and the mixture wasfurther stirred at room temperature for 2 hours. After washing thereaction solution with 1N aqueous solution of hydrochloric acid (20 mL),aqueous solution (10 mL) of sodium hydrogen carbonate (0.84 g) andmethyl chlorocarbonate (0.62 g) were added to the separated organiclayer and the mixture was stirred at 50° C. for 2 hours. The organiclayer was separated, to which 4-heptafluoroisopropyl-2-methylaniline(1.24 g) and concentrated hydrochloric acid (6 drops) were added, andstirred at 50° C. for 1 hour.

After the reaction solution was naturally cooled to room temperature,the solvent was distilled off under reduced pressure and the obtainedresidue was purified by silica gel column chromatography (gradientelution n-hexane/ethyl acetate=2/1 to 1/1) to obtainN¹-(4-heptafluoroisopropyl-2-methylphenyl)-N²-[1-methyl-2-(methylthio)-ethyl]-3-methanesulfonyloxyphthalamide(1.30 g) having the melting point of 101–103° C.

Synthesis Example 4

To an acetonitrile solution (10 mL) ofN-(4-heptafluoroisopropyl-2-methylphenyl)-6-methanesulfonyloxyphthalisoimide(0.45 g), isopropylamine (0.06 g) was added and the mixture was stirredat room temperature for 2 days. After finishing the reaction, thesolvent was distilled off under reduced pressure and the obtainedresidue was purified by silica gel column chromatography (gradientelution n-hexane/ethyl acetate=2/1 to 1/1) to obtain the same compoundas in Synthesis Example 1 (0.13 g).

Synthesis Example 5

To a 1,2-dichloroethane (10 mL) solution ofN²-[1,1-dimethyl-2-(methylthio)ethyl]-N¹-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalamide(0.6 g), hydrogen peroxide (0.54 g), formic acid (0.03 g) and water (1mL) were added and the mixture was stirred at 50° C. for 4 hours. Afternaturally cooling it to room temperature, the organic layer wasconsecutively washed with aqueous solution of sodium thiosulfate andsaturated aqueous solution of sodium chloride and dried with anhydroussodium sulfate. After distilling off the solvent, the obtained residuewas purified by silica gel column chromatography (gradient elutionn-hexane/ethyl acetate=3/1 to 1/1) to obtainN²-[1,1-dimethyl-2-(methylsulfinyl)ethyl]-N¹-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalamide(0.59 g) having the melting point of 85–88° C.

Synthesis Example 6

To a dichloroethane solution (10 mL) ofN²-[1,1-dimethyl-2-(methylthio)ethyl]-N¹-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalamide(0.51 g), m-chloroperbenzoic acid (0.36 g) was added and the mixture wasstirred at room temperature for 5 hours. After finishing the reaction,the reaction solution was consecutively washed with aqueous solution ofsodium thiosulfate, saturated aqueous solution of sodium bicarbonate andsaturated aqueous solution of sodium chloride and dried with anhydroussodium sulfate. After distilling off the solvent, the obtained residuewas purified by silica gel column chromatography (gradient elutionn-hexane/ethyl acetate=2/1 to 1/1) to obtainN²-[1,1-dimethyl-2-(methylsulfonyl)ethyl]-N¹-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalamide(0.41 g) having the melting point of 93–97° C.

The compounds obtained in the same manner to the above-mentionedSynthesis Examples 1 to 6 are shown in the following Table 1, togetherwith the compounds synthesized in Synthesis Examples 1 to 6.

TABLE 1

No. R¹ R² R³ R⁴ R⁵ MP/° C. 1 CH₃ CH(CH₃)₂ CH₃ CF(CF₃)₂ H 168–170 2 CH₃CH(CH₃)CH₂CH₃ CH₃ CF(CF₃)₂ H 187–189 3 CH₃ C(CH₃)₃ CH₃ CF(CF₃)₂ H119–121 4 CH₃ cyclopropyl CH₃ CF(CF₃)₂ H * 5 CH₃ CH(CH₃)CH₂SCH₃ HCF(CF₃)₂ H 181–182 6 CH₃ CH(CH₃)CH₂SCH₃ CH₃ OCF₃ H 129–132 7 CH₃CH(CH₃)CH₂SCH₃ CH₃ CF(CF₃)₂ H 101–103 8 CH₃ CH(CH₃)CH₂SOCH₃ CH₃ CF(CF₃)₂H 221–223 9 CH₃ CH(CH₃)CH₂SO₂CH₃ CH₃ CF(CF₃)₂ H 102–107 10 CH₃C(CH₃)₂CH₂SCH₃ CH₃ CF(CF₃)₂ H  97–99 11 CH₃ C(CH₃)₂CH₂SOCH₃ CH₃ CF(CF₃)₂H  85–88 12 CH₃ C(CH₃)₂CH₂SO₂CH₃ CH₃ CF(CF₃)₂ H  93–97 13 CH₂CH₃CH(CH₃)₂ CH₃ CF(CF₃)₂ H ** 14 CH₂CH₃ CH(CH₃)CH₂SCH₃ CH₃ CF(CF₃)₂ H112–114 15 CH₂CH₃ CH(CH₃)CH₂SOCH₃ CH₃ CF(CF₃)₂ H 16 CH₂CH₃CH(CH₃)CH₂SO₂CH₃ CH₃ CF(CF₃)₂ H 194–196 17 CH₂CH₃ C(CH₃)₂CH₂SCH₃ CH₃CF(CF₃)₂ H  86–91 18 CH₂CH₃ C(CH₃)₂CH₂SOCH₃ CH₃ CF(CF₃)₂ H *** 19 CH₂CH₃C(CH₃)₂CH₂SO₂CH₃ CH₃ CF(CF₃)₂ H  85–89 20 CF₃ CH(CH₃)₂ CH₃ CF(CF₃)₂ H 21CF₃ CH(CH₃)CH₂SCH₃ CH₃ CF(CF₃)₂ H 209–214 22 CF₃ CH(CH₃)CH₂SOCH₃ CH₃CF(CF₃)₂ H 23 CF₃ CH(CH₃)CH₂SO₂CH₃ CH₃ CF(CF₃)₂ H 136–138 24 CH₃C(CH₃)₂CH₂SCH₃ Cl Cl 3-Cl 193–195 25 CH₃ C(CH₃)₂CH₂SOCH₃ Cl Cl 3-Cl135–140 26 CH₃ C(CH₃)₂CH₂SO₂CH₃ Cl Cl 3-Cl 200–203 * ¹H-NMR (CDCl₃,ppm): 0.5–0.8 (4H, m), 2.3 (3H, s), 2.8 (1H, m), 3.2 (3H, s), 6.5 (1H,bs), 6.7 (1H, d), 7.3–7.7 (4H, m), 8.1 (1H, d), 8.4 (1H, bs). ** ¹H-NMR(CDCl₃, ppm): 1.6 (9H, m), 2.1 (3H, s), 2.4 (3H, s), 3.0 (2H, m), 3.5(3H, q), 6.9 (1H, bs), 7.4–7.6 (4H, m), 8.2 (1H, d), 8.4 (1H, bs). ***¹H-NMR (CDCl₃, ppm): 1.2 (6H, d), 1.5 (3H, t), 2.4 (3H, s), 3.4 (2H, q),4.2 (1H, m), 6.2 (1H, bd), 7.4–7.7 (5H, m), 8.2 (1H, bd), 8.5 (1H, bs).

Referential Example 1

To a tetrahydrofuran solution (50 mL) ofN-(4-heptafluoroisopropyl-2-methylphenyl)-3-hydroxyphthalimide (3.60 g)and triethylamine (1.73 g), methanesulfonyl chloride (1.18 g) was addeddrop by drop under ice cooling and the mixture was stirred at roomtemperature for 8 hours. After finishing the reaction, the solvent wasdistilled off under reduced pressure and the obtained residue wasdissolved in ethyl acetate (50 mL), washed consecutively with 2Nhydrochloric acid and saturated aqueous solution of sodium chloride anddried with anhydrous sodium sulfate. After distilling off the solventunder reduced pressure, the crude product was washed with a mixedsolvent of ether and n-hexane to obtainN-(4-heptafluoroisopropyl-2-methylphenyl)-3-methanesulfonyloxyphthalimide(4.04 g) having the melting point of 154–155° C.

Referential Example 2

3-Hydroxyphthalic anhydride (7.29 g) and4-heptafluoroisopropyl-2-methylaniline (12.22 g) in acetic acid (100 mL)were refluxed for 6 hours. After finishing the reaction, the solvent wasdistilled off under reduced pressure and the obtained residue was washedwith a mixed solvent of ether and n-hexane to obtainN-(4-heptafluoroisopropyl-2-methylphenyl)-3-hydroxyphthalimide (11.23 g)having the melting point of 180–182° C.

Referential Example 3

To a toluene solution (20 mL) ofN-isopropyl-3-methanesulfonyl-oxyphthalamic acid (1.80 g),trifluoroacetic anhydride (3.76 g) was added and the mixture was stirredat room temperature for 1 hour. After finishing the reaction, thesolvent and the excess of trifluoroacetic anhydride were distilled offunder reduced pressure to obtainN-isopropyl-6-methanesulfonyloxyphthalisoimide (1.68 g). The obtainedobject was used for the next reaction without purification.

Referential Example 4

Isopropylamine (0.78 g) was added to an acetonitrile solution (10 mL) of3-methanesulfonyloxyphthalic anhydride (1.60 g) under ice cooling andthe mixture was further stirred at room temperature for 8 hours. Afterfinishing the reaction, the solvent and the excess of isopropylaminewere distilled off under reduced pressure and the obtained crude productwas washed with a small amount of acetonitrile to obtainN-isopropyl-3-methanesulfonyloxyphthalamic acid (1.80 g) having themelting point of 56–59° C.

Referential Example 5

Triethylamine (0.83 g) and methanesulfonyl chloride (0.89 g) were addedto a THF solution (10 mL) of 3-hydroxyphthalic anhydride (1.22 g) underice cooling and the mixture was stirred at room temperature for 8 hours.After finishing the reaction, ether (20 mL) was added and the mixturewas washed consecutively with water and saturated aqueous solution ofsodium chloride and dried with anhydrous sodium sulfate. Afterdistilling off the solvent under reduced pressure, the crude product waswashed with a mixed solvent of ether and n-hexane to obtain3-methanesulfonyloxyphthalic anhydride (1.75 g) having the melting pointof 134–140° C.

Referential Example 6

To a 1,2-dichloroethane solution (30 mL) ofN-(4-heptafluoroisopropyl-2-methylphenyl)-6-methanesulfonyloxyphthalamicacid (1.01 g), an aqueous solution (5mL) of sodium hydrogen carbonate(0.27 g) and methyl chlorocarbonate (0.24 g) were consecutively addedand the mixture was stirred at 50° C. for 3 hours. After finishing thereaction, the organic layer was separated and dried with anhydroussodium sulfate. Then the solvent was distilled off under reducedpressure to obtain N-(4-heptafluoro isopropyl-2-methylphenyl)-6-methanesulfonyloxyphthalisoimide (0.49 g)having the refractive index n_(D) ²⁰ 1.4430.

Referential Example 7

To an acetonitrile solution (10 mL) of 3-methanesulfonyloxyphthalicanhydride (0.51 g), 4-heptafluoroisopropyl-2-methylaniline (0.58 g) wasadded drop by drop under ice cooling and the mixture was stirred at roomtemperature for 4 hours. After finishing the reaction, the solvent wasdistilled off under reduced pressure and the obtained crude product waswashed with a small amount of acetonitrile to obtainN-(4-heptafluoroisopropyl-2-methylphenyl)-6-methanesulfonyloxyphthalamicacid (1.01 g) having the melting point of 64–68° C.

USE EXAMPLES Biological Test Example 1

Test against larva of Spodoptera litura

Preparation of test agent:

Solvent: Dimethylformamide 3 parts by weight Emulsifier: Polyoxyethylenealkyl phenyl ether 1 part by weight

In order to make an appropriate formulation of an active compound 1 partby weight of the active compound was mixed with the above-mentionedamount of solvent containing the above-mentioned amount of emulsifierand the mixture was diluted with water to a prescribed concentration.

Test Method:

Leaves of sweet potato were soaked in the test agent diluted to aprescribed concentration with water, dried in the air and put in a dishof 9 cm diameter. 10 larvae of Spodoptera litura at the third instarwere placed on the leaves and kept in a room at constant temperature of25° C. After 2 and 4 days further leaves of sweet potato were added andafter 7 days the number of dead larvae was counted and the rate of deathwas calculated.

In this test the results of 2 dishes at 1 section were averaged.

Test Results

As specific examples the compounds of the compound no. 1, 2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 19, 21, 23, 24, 25 and 26showed 100% of rate of death at 20 ppm concentration of effectivecomponent.

Biological Test Example 2

Test Against Larva of Cnaphalocrocis medinalis Guenee

Test Method:

Root parts of paddy rice (variety: Tamanishiki) cultivated to 4 to 5leaf stage were put in a brown bottle filled with the diluted aqueoussolution of the prescribed concentration of the active compound preparedin the same manner as in the above-mentioned Biological Test Example 1.Three days after the treatment with the agent, ⅓ amount of rice plantwas collected and their foliage part was cut in 4 to 5 cm length, whichwere put in a dish with 9 cm diameter with a sheet of filter paperwetted with 2 mL of water. Five larvae of Cnaphalocrocis medinalisGuenee at the second instar were put in the dish which was placed in aroom at constant temperature of 25° C. After 2 and 4 days, each rest(each ⅓ amount) of foliage parts of rice plant were cut in the samemanner and added to the dish. After 7 days the number of dead larvae wascounted and the rate of death was calculated. In this test the resultsof 2 dishes at 1 section were averaged.

Test Results

As specific examples the compounds of the compound no. 1, 5, 7, 8, 9,10, 11 and 12 showed 100% of rate of death at 20 ppm concentration ofeffective component.

Formulation Example 1 (Granule)

To a mixture of 10 parts of the compound of the present invention (No.1), 30 parts of bentonite (montmorillonite), 58 parts of talc and 2parts of ligninsulfonate salt, 25 parts of water are added, wellkneaded, made into granules of 10 to 40 mesh by an extrusion granulatorand dried at 40 to 50° C. to obtain granules.

Formulation Example 2 (Granules)

Ninety-five (95) parts of clay mineral particles having particlediameter distribution in the range of 0.2 to 2 mm are put in a rotarymixer. While rotating it, 5 parts of the compound of the presentinvention (No. 5) are sprayed together with a liquid diluent, wetteduniformly and dried at 40 to 50° C. to obtain granules.

Formulation Example 3 (Emulsifiable Concentrate)

Thirty (30) parts of the compound of the present invention (No. 11), 55parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7parts of calcium alkylbenzenesulfonate are mixed and stirred to obtainan emulsifiable concentrate.

Formulation Example 4 (Wettable Powder)

Fifteen (15) parts of the compound of the present invention (No. 17), 80parts of a mixture of white carbon (hydrous amorphous silicon oxide finepowders) and powder clay (1:5), 2 parts of sodium alkylbenzenesulfonateand 3 parts of sodium alkylnaphthalenesulfonate-formalin-condensate arecrushed and mixed to make a wettable powder.

Formulation Example 5 (Water Dispersible Granule)

Twenty (20) parts of the compound of the present invention (No. 8), 30parts of sodium ligninsulfonate, 15 parts of bentonite and 35 parts ofcalcined diatomaceous earth are well mixed, added with water, extrudedwith 0.3 mm screen and dried to obtain water dispersible granules.

1. A phthalamide derivative of formula (I)

wherein R¹ represents alkyl that is optionally halogen-substituted, R²represents alkyl that is optionally substituted or cycloalkyl that isoptionally substituted, R³ represents hydrogen, halogen, or alkyl thatis optionally halogen-substituted, R⁴ represents hydrogen,halogen-substituted alkyl, halogen-substituted alkoxy,halogen-substituted phenyl, or halogen-substituted phenoxy, and R⁵represents hydrogen, halogen, or alkyl that is optionallyhalogen-substituted.
 2. A compound according to claim 1 wherein R¹represents C₁₋₆ alkyl that is optionally fluoro-substituted,chloro-substituted, or bromo-substituted, R² represents C₁₋₆ alkyl thatis optionally fluoro-substituted, chloro-substituted, bromo-substituted,C₁₋₄ alkoxy-substituted, C₁₋₄ alkylthio-substituted, C₁₋₄alkylsulfinyl-substituted, or C₁₋₄ alkylsulfonyl-substituted; orrepresents C₃₋₆ cycloalkyl that is optionally halogen-substituted orC₁₋₄ alkyl-substituted, R³ represents hydrogen or halogen; or representsC₁₋₆ alkyl that is optionally fluoro-substituted, chloro-substituted, orbromo-substituted, R⁴ represents hydrogen, halogen-substituted C₁₋₆alkyl, halogen-substituted C₁₋₆ alkoxy, halogen-substituted phenyl, orhalogen-substituted phenoxy, and R⁵ represents hydrogen or halogen; orrepresents C₁₋₆ alkyl that is optionally fluoro-substituted,chloro-substituted, or bromo-substituted.
 3. A compound according toclaim 1 wherein R¹ represents methyl, ethyl, propyl, or trifluoromethyl,R² represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl,n-hexyl, isohexyl, sec-hexyl, methylthiomethyl, ethylthiomethyl,methylthioethyl, ethylthioethyl, methylthiopropyl, ethylthiopropyl,methylthiobutyl, ethylthiobutyl, methylthiopentyl, ethylthiopentyl,methylsulfinylmethyl, ethylsulfinylmethyl, methylsulfinylethyl,ethylsulfinylethyl, methylsulfinylpropyl, ethylsulfinylpropyl,methylsulfinylbutyl, ethylsulfinylbutyl, methylsulfinylpentyl,ethylsulfinylpentyl, methylsulfonylmethyl, ethylsulfonylmethyl,methylsulfonylethyl, ethylsulfonylethyl, methylsulfonylpropyl,ethylsulfonylpropyl, methylsulfonylbutyl, ethylsulfonylbutyl,methylsulfonylpentyl, or ethylsulfonylpentyl; or represents cyclopropyl,cyclobutyl, cyclopentyl, or cyclohexyl, each of which is optionallysubstituted with fluoro, chloro, bromo, methyl, or ethyl, R³ representshydrogen, fluoro, chloro, bromo, methyl, ethyl, or trifluoromethyl, R⁴represents fluoro, chloro, or bromo; or represents methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy,ethoxy, n-propoxy, or isopropoxy, each of which is optionallysubstituted with one or more fluoro, perfluoro-substituted, orsubstituted with one or more fluoro and 1 or 2 chloro, and R⁵ representshydrogen, fluoro, chloro, or bromo; or represents methyl or ethyl, eachof which is optionally fluoro-substituted or chloro-substituted.
 4. Acompound according to claim 1 wherein R¹ represents methyl or ethyl, R2represents isopropyl, tert-butyl, 1-methyl-2-(methylthio)ethyl,1,1-dimethyl-2-(methylthio)ethyl, 1-methyl-2-(methylsulfinyl)ethyl,1,1-d imethyl-2-(methylsulfinyl)ethyl, 1-methyl-2-(methylsulfonyl)ethyl,or 1,1-d imethyl-2-(methylsulfonyl)ethyl, R³ represents methyl, R⁴represents perfluoroisopropyl, and R⁵ represents hydrogen.
 5. A processfor the preparation of a compounds of formula (I) according to claim 1comprising (a) reacting a compound of formula (II)

wherein R¹, R³, R⁴, and R⁵ have the same definitions as for formula (I)of claim 1, with a compound of formula (III)H₂N—R²  (III) wherein R² has the same definition as for formula (I) inclaim 1, in the presence of inert solvents and optionally in thepresence of a base, or (b) reacting a compound of formula (IV)

wherein R¹ and R² have the same definitions as for formula (I) in claim1, with a compound of formula (V)

wherein R³, R⁴, and R⁵ have the same definitions as for formula (I) inclaim 1, in the presence of inert solvents and optionally in thepresence of an acid catalyst, or (c) reacting a compound of formula (VI)

wherein R¹, R³, R⁴, and R⁵ have the same definitions as for formula (I)in claim 1, with a compound of formula (III),H₂N—R²  (III) wherein R² has the same definition as for formula (I) inclaim 1, in the presence of inert solvents and optionally in thepresence of a acid catalyst, or (d) for compounds of formula (I) inwhich R² represents alkylsulfinylalkyl or alkylsulfonylalkyl, reacting acompound of formula (Id)

wherein R^(2d) represents alkyithioalkyl, and R¹, R³, R⁴, and R⁵ havethe same definitions as for formula (I) in claim 1, with an oxidizingagent in the presence of inert solvents.
 6. An insecticidal compositioncontaining one or more phthalamide derivatives of formula (I) accordingto claim
 1. 7. A process for combating insects comprising allowing aneffective amount of one or more phthalamide derivatives of formula (I)according to claim 1 to act on the insects and/or their habitat.
 8. Aprocess for the preparation of insecticidal compositions comprisingmixing one or more phthalamide derivatives of formula (I) according toclaim 1 with one or more extenders and/or surface active agents.